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We report the observation by scanning tunneling microscopy (STM) and low energy atom diffraction, of new, striped, structures at the surface of monolayers of n‐alkane thiols [CH₃ (CH₂)_n−1 SH with n=8,10,12] self‐assembled on the (111) face of single crystal gold. These structures can be prepared by slow (room temperature) or thermally accelerated treatment of the well known c(4√3×2√3)R 30° phase formed by self‐assembly in solution, or can be accessed directly by molecular beam deposition. With respect to the unit mesh of the gold substrate, the new striped structures can be described as p×√3 overlayers where 7.5≤p≤13. The discovery of these phases has implications for the understanding of the growth mechanisms and the pursuit of applications of this widely studied class of materials.